EP3794094A1 - Reciprocating compressor oil - Google Patents

Reciprocating compressor oil

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Publication number
EP3794094A1
EP3794094A1 EP19725127.5A EP19725127A EP3794094A1 EP 3794094 A1 EP3794094 A1 EP 3794094A1 EP 19725127 A EP19725127 A EP 19725127A EP 3794094 A1 EP3794094 A1 EP 3794094A1
Authority
EP
European Patent Office
Prior art keywords
mass
oil
additive
tert
amount
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19725127.5A
Other languages
German (de)
French (fr)
Other versions
EP3794094B1 (en
Inventor
Mai KITAGAWA
Hiroshi Kaneko
Mitsuhiro Nagakari
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of EP3794094A1 publication Critical patent/EP3794094A1/en
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • the present invention relates to a lubricating oil composition and particularly relates to a reciprocating compressor oil.
  • a compressor is a machine that compresses air such as gas and increases its pressure. This compressor is broadly classified into three types: a reciprocating type
  • the reciprocating piston compresses the gas in the cylinder, so the
  • the reciprocating compressor oil required to have an extremely important performance that no carbon is produced. Also, in order to be able to withstand the above high temperature and high pressure, it is necessary for reciprocating compressor oil to have high thermal stability/oxidation stability and to reduce generation of sludge. In addition, when used in cold regions or
  • pour point is also required to be low.
  • the present invention intends to provide a
  • reciprocating compressor oil which can withstand high temperature and high pressure, generate little sludge and can be stably used over a long period of time by obtaining sufficient oxidation stability by selection of base oil and addition of additives .
  • the inventors conducted various studies on additives having effective antioxidant performance in compressor oil and carried out research. As a result, they found that using 2, 6-di-tert-butylphenol and tris (2, 4-di -tert- butylphenyl) phosphite in combination has very good results. Thus, the present invention has been completed based on these findings.
  • the present invention relates to the reciprocating compressor oil, wherein 2, 6-di-tert- butylphenol and tris (2, 4-di-tert-butylphenyl) phosphite are added in combination to the base oil.
  • 2, 6-di-tert-butylphenol is effective when it is contained in an amount of between 0.5 mass% and 6.0 mass% based on the total amount of the compressor oil
  • tris (2, 4-di-tert-butylphenyl) phosphite is effective when it is contained in an amount of between 0.3 mass % and 2.0 mass % based on the total amount of the compressor oil.
  • an alkaline earth metal salt of alkylsalicylic acid in combination as an additive is even more effective.
  • the amount thereof used is preferably between 0.05 mass% and 2.0 mass% based on the total amount.
  • the base oil of the compressor oil uses mineral oil and/or synthetic oil, but it is preferable that the base oil contains a relatively large amount of naphthene.
  • the naphthene content in the total amount of the base oil is about 17 to 30%, preferably 18 to 28%, more preferably 20 to 25% in the %CN of ring analysis according to ASTM D3238.
  • the base oil of the reciprocating compressor oil of the present invention uses mineral oil or synthetic oil.
  • base oils of Group 1, Group 2, Group 3, Group 4 and the like are used, but these base oils can be appropriately mixed and used.
  • the oil containing a relatively large amount of naphthene is preferable, and the naphthene content in the total amount of the base oil is preferably from about 17% to 30% in %C N of the ring analysis according to ASTM D3238. Further, it is preferably from 18 to 28%, more preferably from 20 to 25%.
  • the naphthene- containing base oil has high solubility in additives and sludge as compared with the base oil containing a large amount of paraffin, so it is especially useful when used for the reciprocating compressor oil since the deposit (carbon deposit) is soft even when it is carbonized.
  • the proportion of naphthene component When the proportion of naphthene component is small, carbonization tends to occur, and the generated carbon becomes hard and deposits and sticks, which tends to cause malfunction of the compressor and the like.
  • the naphthene component when the naphthene component is excessive, since the naphthene component is highly volatile, the base oil evaporates during use and increases the kinematic viscosity of the lubricating oil, which is not preferable.
  • the content of the naphthene component in the total amount of the base oil has an appropriate range, and it is preferable to set the above ratio.
  • 2, 6-di-tert-butylphenol is added to the base oil and used.
  • This 2, 6-di-tert-butylphenol is a phenolic substance having the structure shown below.
  • This 2, 6-di-tert-butylphenol is widely known as an antioxidant and has a structure similar to the widely used BHT (butylhydroxytoluene) (2, 6-di-tert-butyl-4- methylphenol) described below. It lacks the methyl group at the 4-position of the benzene ring of BHT.
  • BHT butylhydroxytoluene
  • 6-di-tert-butylphenol is known as phenolic substance having a structure similar to BHT and 4, 4 ' -methylenebis (2, 6-di-tert-butylphenol) [2, 2', 6,
  • the 2, 6-di-tert-butylphenol exists in a state of forming a dimer due to the fact that the 4-position of the benzene ring is a hydrogen atom as described above, and is difficult to sublimate.
  • the 4-position of the benzene ring is a hydrogen atom as described above, and is difficult to sublimate.
  • Such a 2, 6-di-tert-butylphenol is used in an amount of between 0.5 mass% and 6.0 mass%, preferably between 1.0 mass% and 5.0 mass%, based on the total amount of the compressor oil.
  • This 2, 6-di-tert-butylphenol is used in combination with tris (2, 4-di-tert-butylphenyl) phosphite which is a phosphate ester-based antioxidant as an additive.
  • the tris (2, 4-di-tert-butylphenyl) phosphite is also used in an amount of between 0.3 mass% and 2.0 mass%, preferably in the range of from 0.5 mass% to 1.0 mass%, based on the total amount.
  • Alkaline earth metal salt of alkylsalicylic acid in combination with this compressor oil as an additive is even more effective.
  • Alkaline earth metals thereof include calcium, magnesium and the like, but in general, Ca salicylate is often used.
  • the amount thereof used is preferably between 0.05 mass% and 2.0 mass%, preferably from 0.075 mass% to 1.5 mass%, and more preferably from 0.075 mass% to 1.0 mass%, based on the total amount.
  • the compressor oil may contain known additives if necessary, for example, extreme pressure agents, rust preventive agents, demulsifiers, copper deactivators, antiwear agents, dispersants, friction modifiers, corrosion inhibitors, pour point depressants, antifoaming agents and various other additives. These additives may be blended singly or in combination of several kinds. In this case, an additive package not containing an antioxidant or a detergent dispersant may be used.
  • the pour point (pour point measured by the method described in JIS K 2269) of the reciprocating compressor oil according to the present invention is preferably -30 °C. or lower, more preferably -35 °C. or lower.
  • a low pour point indicates that the lubricating oil composition is excellent in low temperature characteristics.
  • Base oil 1 Fischer-Tropsch base oil by gas-to-liquid method (Properties and the like: Kinematic viscosity at 40°C.; 17.1 mm 2 /s, Kinematic viscosity at 100°C.; 4.0 m 2 /s, Viscosity index; 135, density at 15°C.; 0.814 g/cm 3 , %C A of ring analysis according to ASTM D 3238 method; 0%, %C N of ring analysis according to ASTM D 3238 method; 8%, and % C P of ring analysis according to ASTM D 3238 method; 92%)
  • Base oil 2 Purified mineral oil belonging to Group I (Properties and the like: Kinematic viscosity at 40°C.;
  • Viscosity index 107, Density at 15 °C.; 0.863 g/cm 3 , %C A of ring analysis according to ASTM D 3238 method; 3%, %C N of ring analysis according to ASTM D 3238 method; 28%, and %C P of ring analysis according to ASTM D 3238 method; 69%)
  • Base oil 3 Purified mineral oil belonging to Group I (Properties and the like: Kinematic viscosity at 40°C.;
  • Viscosity index 106, Density at 15 °C. ; 0.875 g/cm 3 , %C A of ring analysis according to ASTM D 3238 method; 4%, %C N of ring analysis according to ASTM D 3238 method; 27%, and %C P of ring analysis according to ASTM D 3238 method; 69%)
  • Base oil 4 Naphthenic base oil (Properties and the like; Kinematic viscosity at 40°C.; 139.1 iran 2 /s, Kinematic viscosity at 100°C.; 10.8 mm 2 /s, Viscosity index; 35,
  • Additive 7 Additive package for compressor oil containing ZnDTP, rust preventive agent, demulsifier and antifoaming agent
  • Compressor oils of Control Examples 1 to 3 were obtained in accordance with the above Experiment Example 1 except for using the compositions shown in Table 1. Test on Preliminary Experiment Example
  • the test was conducted at 120 °C. for 168 hours according to the oxidation stability test (Dry-TOST method) of ASTM D7873.
  • test was conducted at a test temperature of 150 °C. under a pressure of 620 kPa before heating in accordance with JIS K 2514-3 Rotating Bomb Oxidation Stability Test (RPVOT) , and the time from maximum pressure to 175 kPa drop was measured (RPVOT value: min) .
  • RVOT Rotating Bomb Oxidation Stability Test
  • the lubricating oil composition is excellent in oxidation stability as the time is longer.
  • the RPVOT value residual ratio (%) was calculated by the following formula.
  • 2, 6-di-tert-butylphenol was found to be a preferred antioxidant in compressor oil without having problems in sublimability and oxidation stability.
  • Base oil 1 Same as the base oil 1 of the preliminary experiment .
  • Base oil 2 Same as the base oil 2 of the preliminary experiment .
  • Base oil 4 Same as the base oil 4 of the preliminary experiment .
  • Base oil 5 Fischer-Tropsch base oil by gas-to-liquid method (Properties and the like: Kinematic viscosity at 40°C.; 44.9 m 2 /s, Kinematic viscosity at 100°C.; 7.7 mm 2 /s, Viscosity index; 142, Density at 15 °C. ; 0.828 g/cm 3 , %C 3 ⁇ 4 of ring analysis according to ASTM D 3238 method; 0%, %C N of ring analysis according to ASTM D 3238 method; 8%, and %Cp of ring analysis according to ASTM D 3238 method; 92%)
  • Additive 7 Same as additive 7 of the preliminary experiment. (Additive package for compressor oil containing ZnDTP, rust preventive agent, demulsifier and antifoaming agent)
  • Compressor oils of Inventive Examples 2 to 6 were obtained in accordance with Inventive Example 1 except for using the compositions shown in Table 2 and Table 3.
  • Compressor oils of Comparative Examples 1 to 10 were obtained in accordance with Inventive Example 1 except for using the compositions shown in Table 4 and Table 5.
  • the evaluation criteria are as follows.
  • the sludge produced in the compressor oil to be tested was filtered in accordance with the quantitative method and the apparatus (filter pore size: 0.8 pm) described in JIS B 9931 (Method for measuring hydraulic oil contamination by mass method) .
  • the filtered sludge was then washed with n- hexane and the amount of sludge was determined.
  • the evaluation criteria are as follows.
  • pour point was measured in accordance with JIS K 2269.
  • a Panel coking test test was conducted in accordance with the U.S. Federal District Engineering Mutual Statement 791-3462, wherein the test oil with an oil temperature set at 90 °C. was splashed with a rotating splasher over 12 hours at intervals of rotation time of 1 second/stop time of 14 seconds on an aluminum panel heated and set to a specified temperature of 270 °C. This test was conducted to evaluate the suppression performance of the test oil to suppress deposit formation, namely, cleanliness, from weight increase of panel before and after test.
  • Example 1 As a result, the sludge amount after ISOT showed excellent results ( ⁇ ) , and the performance was further improved.
  • Comparative Example 3 the additive 2 in Inventive Example 1 was used, and the additive 1 was not used.
  • the acid value after ISOT was also poor and the amount of sludge was also very large, which are not favorable results.
  • Comparative Example 4 the amount of the additive 2 used in Comparative Example 3 was increased to 3.0 mass%.
  • the acid value after ISOT was improved, but the amount of sludge was not yet satisfactory, which is not preferable .
  • Comparative Example 6 1.0 mass% of additive 2 and 0.075 mass% of additive 3 were added to the composition of Comparative Example 5. As a result, the amount of sludge decreased and showed good result ( (O) ) , but the acid value was poor (X); thus, good results were not obtained.
  • Comparative Example 8 the amount of the base oil 4 and base oil 1 of Comparative Example 7 was 75.0 mass% and 22.74 mass%. The naphthene content was high, and excellent results ( ⁇ ) were obtained in the panel coking test.
  • the base oil 2 was used in place of base oil 1 and base oil 5 of Example 4, and its use amount was increased to 54.41 mass%.
  • the naphthene content was high, the acid value and the numerical value of sludge amount after ISOT and the panel coking test were excellent, but the pour point increased causing problem in use at low temperature.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The invention provides a compressor oil, wherein 2, 6-di-tert-butylphenol and tris (2, 4-di-tert-butylphenyl) phosphite are added to a base oil having a naphthene content of from 17 to 30% based on the total amount of the base oil, and has a pour point of -25°C. or lower. 2, 6-di-tert-butylphenol is effective when it is contained in an amount of from 0.5 mass% to 6.0 mass% based on the total amount of the compressor oil, and tris (2, 4-di-tert-butylphenyl) phosphite is effective when it is contained in an amount of from 0.3 mass % to 2.0 mass % based on the total amount of the compressor oil. Furthermore, adding an alkaline earth metal salt of alkylsalicylic acid in combination is even more effective. The amount thereof used is preferably from 0.05 mass% to 2.0 mass%.

Description

RECIPROCATING COMPRESSOR OIL
Field of the Invention
The present invention relates to a lubricating oil composition and particularly relates to a reciprocating compressor oil.
Background of the Invention
A compressor is a machine that compresses air such as gas and increases its pressure. This compressor is broadly classified into three types: a reciprocating type
(reciprocating type) , a rotating type, and a turbo type. However, lubrication points differ depending on the type, and accordingly the required performance of compressor oil differs .
In the reciprocating compressor, the reciprocating piston compresses the gas in the cylinder, so the
compressor oil used for the reciprocating piston directly contacts the high temperature/high pressure of the
compressed gas and tends to be easily carbonized. If the carbon thus generated adheres to the periphery of the valve, there is a risk of malfunctioning of the valve or risk of ignition or explosion due to heat accumulation of adhered carbon.
Therefore, the reciprocating compressor oil required to have an extremely important performance that no carbon is produced. Also, in order to be able to withstand the above high temperature and high pressure, it is necessary for reciprocating compressor oil to have high thermal stability/oxidation stability and to reduce generation of sludge. In addition, when used in cold regions or
outdoors, it is necessary to be stable even at low
temperatures, so pour point is also required to be low.
Conventionally, phosphorus-based antioxidants, amine- based antioxidants, phenol-based antioxidants, and the like have been used as additives in order to meet the demand in such compressor oil, as in JPH11-189781.
The present invention intends to provide a
reciprocating compressor oil which can withstand high temperature and high pressure, generate little sludge and can be stably used over a long period of time by obtaining sufficient oxidation stability by selection of base oil and addition of additives .
Summary of the Invention
The inventors conducted various studies on additives having effective antioxidant performance in compressor oil and carried out research. As a result, they found that using 2, 6-di-tert-butylphenol and tris (2, 4-di -tert- butylphenyl) phosphite in combination has very good results. Thus, the present invention has been completed based on these findings.
In other words, the present invention relates to the reciprocating compressor oil, wherein 2, 6-di-tert- butylphenol and tris (2, 4-di-tert-butylphenyl) phosphite are added in combination to the base oil.
As additive, 2, 6-di-tert-butylphenol is effective when it is contained in an amount of between 0.5 mass% and 6.0 mass% based on the total amount of the compressor oil, and tris (2, 4-di-tert-butylphenyl) phosphite is effective when it is contained in an amount of between 0.3 mass % and 2.0 mass % based on the total amount of the compressor oil.
In addition, using an alkaline earth metal salt of alkylsalicylic acid in combination as an additive is even more effective. The amount thereof used is preferably between 0.05 mass% and 2.0 mass% based on the total amount.
The base oil of the compressor oil uses mineral oil and/or synthetic oil, but it is preferable that the base oil contains a relatively large amount of naphthene. The naphthene content in the total amount of the base oil is about 17 to 30%, preferably 18 to 28%, more preferably 20 to 25% in the %CN of ring analysis according to ASTM D3238. Detailed Description of the Invention
According to the present invention, even when the oil is used under conditions of high temperature and high pressure, its antioxidant performance is excellent, the production of sludge is small, the formation of sediments in oil is small, and it can be stably used over a long period of time. The base oil of the reciprocating compressor oil of the present invention uses mineral oil or synthetic oil.
In the base oil classification of API, base oils of Group 1, Group 2, Group 3, Group 4 and the like are used, but these base oils can be appropriately mixed and used.
As this base oil, the oil containing a relatively large amount of naphthene is preferable, and the naphthene content in the total amount of the base oil is preferably from about 17% to 30% in %CN of the ring analysis according to ASTM D3238. Further, it is preferably from 18 to 28%, more preferably from 20 to 25%.
As described in the patent literature, the naphthene- containing base oil has high solubility in additives and sludge as compared with the base oil containing a large amount of paraffin, so it is especially useful when used for the reciprocating compressor oil since the deposit (carbon deposit) is soft even when it is carbonized.
When the proportion of naphthene component is small, carbonization tends to occur, and the generated carbon becomes hard and deposits and sticks, which tends to cause malfunction of the compressor and the like. On the other hand, when the naphthene component is excessive, since the naphthene component is highly volatile, the base oil evaporates during use and increases the kinematic viscosity of the lubricating oil, which is not preferable. Thus, the content of the naphthene component in the total amount of the base oil has an appropriate range, and it is preferable to set the above ratio.
As described above, 2, 6-di-tert-butylphenol is added to the base oil and used. This 2, 6-di-tert-butylphenol is a phenolic substance having the structure shown below.
Chemical formula 1 :
This 2, 6-di-tert-butylphenol is widely known as an antioxidant and has a structure similar to the widely used BHT (butylhydroxytoluene) (2, 6-di-tert-butyl-4- methylphenol) described below. It lacks the methyl group at the 4-position of the benzene ring of BHT.
Chemical formula 2 :
Also, it has a structure similar to the following 4,
4 ' -methylenebis (2 , 6-di-tert-butylphenol) which is widely used and also widely known as antioxidant.
Chemical formula 3 :
As mentioned above, 2, 6-di-tert-butylphenol is known as phenolic substance having a structure similar to BHT and 4, 4 ' -methylenebis (2, 6-di-tert-butylphenol) [2, 2', 6,
6 ' -tetra-tert-butyl-4 , 4 ' -methylenediphenol] . However, there is concern of sublimability, but the inventors found excellent oxidation preventing performance in the present invention.
Further, the 4, 4 ' -methylene bis (2, 6-di-tert- butylphenol) is hardly decomposable and highly
concentrated, so it is sometimes designated under a
Monitoring Chemical Substance as its long-term toxicity against humans or higher predatory animals is not clear. Hence, it is effective to avoid use from such aspect as well .
The 2, 6-di-tert-butylphenol exists in a state of forming a dimer due to the fact that the 4-position of the benzene ring is a hydrogen atom as described above, and is difficult to sublimate. In addition, due to the
combination effect (synergistic effect) of the additives, the expression of the dimer antioxidant function could be found.
Such a 2, 6-di-tert-butylphenol is used in an amount of between 0.5 mass% and 6.0 mass%, preferably between 1.0 mass% and 5.0 mass%, based on the total amount of the compressor oil.
This 2, 6-di-tert-butylphenol is used in combination with tris (2, 4-di-tert-butylphenyl) phosphite which is a phosphate ester-based antioxidant as an additive.
Chemical formula 4 :
When used in combination with phosphate ester-based antioxidant, it is possible to obtain a compressor oil having a stable high-temperature and high-pressure
resistance over a long period of time with further improved the antioxidant performance and reduction in generation of sludge.
The tris (2, 4-di-tert-butylphenyl) phosphite is also used in an amount of between 0.3 mass% and 2.0 mass%, preferably in the range of from 0.5 mass% to 1.0 mass%, based on the total amount.
Using this alkaline earth metal salt of alkylsalicylic acid in combination with this compressor oil as an additive is even more effective. Alkaline earth metals thereof include calcium, magnesium and the like, but in general, Ca salicylate is often used. The amount thereof used is preferably between 0.05 mass% and 2.0 mass%, preferably from 0.075 mass% to 1.5 mass%, and more preferably from 0.075 mass% to 1.0 mass%, based on the total amount.
The compressor oil may contain known additives if necessary, for example, extreme pressure agents, rust preventive agents, demulsifiers, copper deactivators, antiwear agents, dispersants, friction modifiers, corrosion inhibitors, pour point depressants, antifoaming agents and various other additives. These additives may be blended singly or in combination of several kinds. In this case, an additive package not containing an antioxidant or a detergent dispersant may be used.
The pour point (pour point measured by the method described in JIS K 2269) of the reciprocating compressor oil according to the present invention is preferably -30 °C. or lower, more preferably -35 °C. or lower. A low pour point indicates that the lubricating oil composition is excellent in low temperature characteristics.
Examples
Preliminary Experiment
Firstly, a preliminary experiment was conducted to select the antioxidant. In the preliminary experiment, the following materials were prepared.
• Base oil 1: Fischer-Tropsch base oil by gas-to-liquid method (Properties and the like: Kinematic viscosity at 40°C.; 17.1 mm2/s, Kinematic viscosity at 100°C.; 4.0 m2/s, Viscosity index; 135, density at 15°C.; 0.814 g/cm3, %CA of ring analysis according to ASTM D 3238 method; 0%, %CN of ring analysis according to ASTM D 3238 method; 8%, and % CP of ring analysis according to ASTM D 3238 method; 92%)
• Base oil 2: Purified mineral oil belonging to Group I (Properties and the like: Kinematic viscosity at 40°C.;
25.1 mm2/s, Kinematic viscosity at 100°C.; 4.7 mm2/s,
Viscosity index; 107, Density at 15 °C.; 0.863 g/cm3, %CA of ring analysis according to ASTM D 3238 method; 3%, %CN of ring analysis according to ASTM D 3238 method; 28%, and %CP of ring analysis according to ASTM D 3238 method; 69%)
• Base oil 3: Purified mineral oil belonging to Group I (Properties and the like: Kinematic viscosity at 40°C.;
53.2 mm2/s, Kinematic viscosity at 100°C.; 7.6 mm2/s,
Viscosity index; 106, Density at 15 °C. ; 0.875 g/cm3, %CA of ring analysis according to ASTM D 3238 method; 4%, %CN of ring analysis according to ASTM D 3238 method; 27%, and %CP of ring analysis according to ASTM D 3238 method; 69%)
• Base oil 4: Naphthenic base oil (Properties and the like; Kinematic viscosity at 40°C.; 139.1 iran2/s, Kinematic viscosity at 100°C.; 10.8 mm2/s, Viscosity index; 35,
Density at 15°C.; 0.918 g/cm3, %CA of ring analysis
according to ASTM D 3238 method; 11%, %CN of ring analysis according to ASTM D 3238 method; 39%, and %CP of ring analysis according to ASTM D 3238 method; 50%) • Additive 1: 2, 6-di-tert-butylphenol
• Additive 2: tris (2, 4-di-tert-butylphenyl) phosphite
• Additive 3: Calcium salicylate
• Additive 4: 4, 4 ' -methylenebis- (2, 6-di-tert- butylphenol)
• Additive 5: BHT (butylhydroxytoluene) (2, 6-di-tert- butyl-4-methylphenol)
• Additive 6: Benzenepropanoic acid 3, 5-bis (1, 1- dimethyl-ethyl) -4-hydroxy-C7 to C9 side chain alkyl ester
• Additive 7 : Additive package for compressor oil containing ZnDTP, rust preventive agent, demulsifier and antifoaming agent
The following Experiment Example and Control
Experiment Examples were then prepared.
Experiment Example 1
1.000 mass% of additive 1, 0.500 mass% of additive 2 and 0.075 mass% of additive 3 were added to a mixed base oil obtained by mixing 24.000 mass% of the base oil 1, 17.000 mass% of the base oil 2, 8.410 mass% of the base oil 3 and 48.330 mass% of the base oil 4. Further, 0.685 mass% of additive 7 was added to the above mixture and mixed well to obtain a compressor oil of Inventive Example 1.
Control Experiment Examples 1 to 3
Compressor oils of Control Examples 1 to 3 were obtained in accordance with the above Experiment Example 1 except for using the compositions shown in Table 1. Test on Preliminary Experiment Example
The following test was conducted to know the
performance of the above Experiment Example and the Control Experiment Examples.
Oxidation Stability Test (Dry-TOST) :
The test was conducted at 120 °C. for 168 hours according to the oxidation stability test (Dry-TOST method) of ASTM D7873.
After the test, the test was conducted at a test temperature of 150 °C. under a pressure of 620 kPa before heating in accordance with JIS K 2514-3 Rotating Bomb Oxidation Stability Test (RPVOT) , and the time from maximum pressure to 175 kPa drop was measured (RPVOT value: min) .
It can be said that the lubricating oil composition is excellent in oxidation stability as the time is longer.
Further, from the RPVOT value (min) after the Dry-TOST test, the RPVOT value residual ratio (%) was calculated by the following formula.
[RPVOT value residual ratio] = [RPVOT value after test / initial RPVOT value] c 100
The criteria for evaluation of oxidation stability are as follows.
The test results for the preliminary experiments are shown in Table 1. Table 1
As shown in Table 1, when 1 mass% of 2, 6-di-tert- butylphenol (Additive 1) of Experiment Example 1 was used, it was found that the RPVOT value after the Dry-TOST test does not decrease from the RPVOT value of the fresh oil, the RPVOT value residual ratio is good, and the oxidation stability is excellent.
On the other hand, in Control Experiment Example 1, when the same amount of 4, 4 ' -methylenebis (2, 6-di-tert- butylphenol) (Additive 4) was used instead of additive 1 in Experiment Example 1, the RPVOT value residual ratio was low, and good results were not obtained.
In Control Experiment Example 2, when the same amount of BHT (Additive 5) was used instead of additive 1 in Experiment Example 1, the residual ratio of RPVOT value was further lower, and good results were not obtained.
In Control Experiment Example 3, when the same amount of benzene propanoic acid 3, 5-bis (1, 1-dimethyl-ethyl) -4- hydroxy-C7 to C9 side chain alkyl ester (additive 6) was used instead of additive 1 in Experiment Example 1, the RPVOT value residual ratio was further lower and good results were not obtained.
In Control Experiment Example 2, adhesion to the condenser was observed by sublimation of BHT (Additive 5) after the Dry-TOST test.
On the other hand, in Experiment Example 1, such adhesion was not observed and it was confirmed that there was no problem concerning the sublimability of 2, 6-di- tert-butylphenol (Additive 1) .
Thus, 2, 6-di-tert-butylphenol was found to be a preferred antioxidant in compressor oil without having problems in sublimability and oxidation stability.
This is because the 2, 6-di-tert-butylphenol exists in a state of forming a dimer called 3, 3', 5, 5 ' -tetra-tert- butyl-4, 4 ' -diphenoquinone of the following formula due to the fact that the 4-position of the benzene ring is a hydrogen atom as described above; hence it is difficult to sublimate. Thus, the expression of the antioxidant function of 3, 3', 5, 5 ' -tetra-tert-butyl-4 , 4'- diphenoquinone could be found by the combination effect
(synergistic effect) of the additives.
Chemical formula 5:
Inventive and Comparative Examples
Based on the above preliminary experiment, the following materials were prepared in order to prepare
Examples and Comparative Examples. In addition, the compressor oil of the present invention will be
specifically described below with reference to Examples and Comparative Examples, but the present invention is not at all limited thereto.
• Base oil 1: Same as the base oil 1 of the preliminary experiment .
• Base oil 2: Same as the base oil 2 of the preliminary experiment .
• Base oil 4: Same as the base oil 4 of the preliminary experiment .
• Base oil 5: Fischer-Tropsch base oil by gas-to-liquid method (Properties and the like: Kinematic viscosity at 40°C.; 44.9 m2/s, Kinematic viscosity at 100°C.; 7.7 mm2/s, Viscosity index; 142, Density at 15 °C. ; 0.828 g/cm3, %C¾ of ring analysis according to ASTM D 3238 method; 0%, %CN of ring analysis according to ASTM D 3238 method; 8%, and %Cp of ring analysis according to ASTM D 3238 method; 92%)
• Additive 1: Same as additive 1 of the preliminary experiment. (2, 6-di-tert-butylphenol)
• Additive 2 : Same as additive 2 of the preliminary experiment. (tris(2, 4-di-tert-butylphenyl) phosphite)
• Additive 3: Same as additive 3 of the preliminary experiment. (Ca Salicylate)
• Additive 4 : Same as additive 4 of the preliminary experiment. ( 4 , 4 ' -methylenebis (2, 6-di-tert-butylphenol) )
• Additive 7 : Same as additive 7 of the preliminary experiment. (Additive package for compressor oil containing ZnDTP, rust preventive agent, demulsifier and antifoaming agent)
The following Inventive Examples and Comparative
Examples were prepared. Inventive Example 1
1.000 mass% of additive 1 and 0.500 mass% of additive 2 were added to a mixed base oil obtained by mixing 32.485 mass% of the base oil 1, 17.000 mass% of the base oil 5 and 48.330 mass% of the base oil 4. Further, 0.685 mass% of the additive 7 was added to the above mixture and mixed well to obtain a compressor oil of Inventive Example 1. Inventive Examples 2 to 6
Compressor oils of Inventive Examples 2 to 6 were obtained in accordance with Inventive Example 1 except for using the compositions shown in Table 2 and Table 3.
Comparative Examples 1 to 10
Compressor oils of Comparative Examples 1 to 10 were obtained in accordance with Inventive Example 1 except for using the compositions shown in Table 4 and Table 5.
Test
The following test was conducted to know the
performance of the Inventive Examples and the Comparative Examples .
An ISOT test (oxidation stability test) was conducted, wherein the test equipment and the test method were in accordance with JIS K 2514, the catalyst was immersed in the sample, and the sample was stirred with a stirring rod for 72 hours at 150 ° C. and oxidized. The acid value after ISOT test was determined by potentiometric titration.
The evaluation criteria are as follows.
For the compressor oil after the above ISOT test, the sludge produced in the compressor oil to be tested was filtered in accordance with the quantitative method and the apparatus (filter pore size: 0.8 pm) described in JIS B 9931 (Method for measuring hydraulic oil contamination by mass method) . The filtered sludge was then washed with n- hexane and the amount of sludge was determined. The evaluation criteria are as follows.
Pour point was measured in accordance with JIS K 2269. A Panel coking test test was conducted in accordance with the U.S. Federal District Engineering Mutual Statement 791-3462, wherein the test oil with an oil temperature set at 90 °C. was splashed with a rotating splasher over 12 hours at intervals of rotation time of 1 second/stop time of 14 seconds on an aluminum panel heated and set to a specified temperature of 270 °C. This test was conducted to evaluate the suppression performance of the test oil to suppress deposit formation, namely, cleanliness, from weight increase of panel before and after test.
The test results are indicated by the weight increase
(mg) of the aluminum panel, and the indices of the
evaluation showing the high temperature cleanliness are as follows .
The results of the tests are shown in Tables 2 to 5.
Note that, in each of the tables, for the test results which are not described, the tests were omitted from the results of other tests.
As shown in Table 2, when 1 mass% of 2, 6-di-tert- butylphenol (additive 1) and 0.5 mass% of tris (2, 4-di- tert-butylphenyl) phosphite (additive 2) were used in Inventive Example 1, good results were obtained, i.e. a reciprocating compressor oil having small increase in the acid value and good sludge amount (O) after the oxidation stability test (ISOT), having low pour point, i.e. -35°C. and good panel coking test result (O) and can withstand high temperature and high pressure, was obtained.
In Inventive Example 2, the use amount of additive 1 and additive 2 was increased to about twice that in
Inventive Example 1. As a result, good results (O) were obtained for both the acid value and the sludge amount after ISOT. Thus, favorable results were obtained.
In Inventive Example 3, the amount of the additive 1 used was changed to 5.0 mass% which is 5 times higher than that of Inventive Example 1, and the amount of the base oil 1 was reduced accordingly. As a result, even more
favorable results were obtained as compared with Inventive Example 1.
In Inventive Example 4 shown in Table 3, 0.075 mass% of Ca salicylate (additive 3) was added to Inventive
Example 1. As a result, the sludge amount after ISOT showed excellent results (©) , and the performance was further improved.
In Inventive Example 5, the amount of Ca salicylate in Inventive Example 4 was increased to 0.5 mass%, and even better results were obtained for the panel coking test.
In Inventive Example 6, the amount of the Ca
salicylate in Inventive Example 4 was further increased to 1.0 mass%. As a result, the compressor oil giving better results as a whole was obtained.
On the other hand, in the Comparative Examples shown in Table 4, the additive 1 in Inventive Example 1 was used and the additive 2 was not used. The acid value after ISOT was good but the amount of sludge was very large; thus, good results were not obtained. In Comparative Example 2, the amount of additive 1 used was increased to 3.0 mass% with respect to Comparative Example 1, but both the acid value and the sludge amount after ISOT were poor, which is not preferable as a reciprocating compressor oil.
In Comparative Example 3, the additive 2 in Inventive Example 1 was used, and the additive 1 was not used. The acid value after ISOT was also poor and the amount of sludge was also very large, which are not favorable results. In Comparative Example 4, the amount of the additive 2 used in Comparative Example 3 was increased to 3.0 mass%. The acid value after ISOT was improved, but the amount of sludge was not yet satisfactory, which is not preferable .
In Comparative Example 5, 1.0 mass% of additive 4, a phenolic antioxidant was used instead of additive 1. As a result, the panel coking test showed good (O) result, but the result of acid value and sludge amount after ISOT was poor (X), which is not preferable.
In Comparative Example 6, 1.0 mass% of additive 2 and 0.075 mass% of additive 3 were added to the composition of Comparative Example 5. As a result, the amount of sludge decreased and showed good result ( (O) ) , but the acid value was poor (X); thus, good results were not obtained.
In Comparative Example 7, the amount of base oil 4 and base oil 1 of Example 4 was high as 90.0 mass%, and 7.74 mass%, respectively, (both based on the total amount) . The naphthene content was high, and excellent results (©) were obtained in the panel coking test. However, the acid value after ISOT was poor and the numerical value of sludge amount was extremely poor. Thus, it is not preferable as compressor oil.
In Comparative Example 8, the amount of the base oil 4 and base oil 1 of Comparative Example 7 was 75.0 mass% and 22.74 mass%. The naphthene content was high, and excellent results (©) were obtained in the panel coking test.
However, the acid value after ISOT was still poor and the numerical value of sludge amount was also extremely poor. Thus, preferable compressor oil was not obtained.
In Comparative Example 9, the amount of base oil 4 of Comparative Example 8 was reduced to 25.0 mass% and the amount of base oil 5 was increased to 50.0 mass%. The naphthene content was low, and extremely poor results were obtained in the panel coking test. Thus, it is not preferable as compressor oil.
In Comparative Example 10, the base oil 2 was used in place of base oil 1 and base oil 5 of Example 4, and its use amount was increased to 54.41 mass%. The naphthene content was high, the acid value and the numerical value of sludge amount after ISOT and the panel coking test were excellent, but the pour point increased causing problem in use at low temperature.
Note that the compressor oil of Experiment Example 1 prepared in the above preliminary test can be used in the same manner as in the above-mentioned Examples .
Table 2
Table 3 Table 4
Table 5

Claims

C L A I M S
1. A reciprocating compressor oil comprising a 2, 6-di- tert-butylphenol and a tris (2, 4-di-tert-butylphenyl) phosphite as additive in a mineral oil and/or a synthetic oil as a base oil, wherein the naphthene component in the total amount of base oil is from 17 to 30% in the %CN of ring analysis according to ASTM D3238, and having a pour point of -25 ° C. or lower.
2. The reciprocating compressor oil according to claim 1, wherein the content of additive 2, 6-di-tert-butylphenol is between 0.5 mass% and 6.0 mass% and the content of additive tris (2, 4-di-tert-butylphenyl) phosphite is between 0.3 mass% and 2.0 mass% based on the total amount of the compressor oil.
3. The reciprocating compressor oil according to claim 1 or 2, wherein the compressor oil further contains 0.05 mass% or more and 2.0 mass% or less of an alkaline earth metal salt of salicylate as an additive based on the total amount of the compressor oil.
4. The reciprocating compressor oil according to claim 3, wherein the alkaline earth metal salt of the salicylate is
Ca salicylate.
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US6172014B1 (en) 1998-06-30 2001-01-09 Pennzoil-Quaker State Method of lubricating compression cylinders used in the manufacture of high-pressure polyethylene
EP1776441A1 (en) 2004-08-18 2007-04-25 Ciba Specialty Chemicals Holding Inc. Lubricating oil compositions with improved performance
US7441596B2 (en) 2006-06-23 2008-10-28 Baker Hughes Incorporated Swelling element packer and installation method
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US20090181871A1 (en) * 2007-12-19 2009-07-16 Chevron U.S.A. Inc. Compressor Lubricant Compositions and Preparation Thereof
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